Esters of 3,7,11 -trimethyldodeca-2,4,11-trienoic acid

ABSTRACT

Novel aliphatic hydrocarbon polyolefinic esters, synthesis thereof, useful for the control of insects.

Henrick et a1.

ESTERS OF 3,7,11 -TRlMETHYLDODECA-2,4,l l-TRIENOIC ACID Inventors: Clive A. Henrick; John B. Siddall,

both of Palo Alto, Calif.

Assignee: Zoecon Corporation, Pa1o Alto,

Calif.

Filed: Nov. 9, 1972 Appl. No.: 305,042

[ May 6, 1975 [56] References Cited UNITED STATES PATENTS 3,666,780 5/1972 Calame 260/405 FOREIGN PATENTS OR APPLICATIONS 2,115,673 10/1971 Germany 1,043,307 11/1958 Germany Primary ExaminerDona1d G. Daus Assistant ExaminerDiana G. Rivers Attorney, Agent, or F irm- Donald W. Erickson; Lee-Louise H. Priest [5 7 ABSTRACT Novel aliphatic hydrocarbon polyolefinic esters, synthesis thereof, useful for the control of insects.

7 Claims, No Drawings 1 2 ESTERS OF 3,7,11 the C-2,3 trans and cis isomers, the C-2,3 transisomer -TRlMETHYLDODECA-2,4,1l-TRIENOIC ACID being the preferred embodiment for the control of insects.

The compounds of formula A are also useful for the This invention relates to novel esters, derivatives 5 preparation f other novel ds, lri f ithe fl 0f Ihfl fofmula AI reactions on the olefinic bonds.

i z 3 P: a CH -C-CH -CH -CH -Cl-i-Cl-l -CH=CH1C=Cl-l-C-R (A) wherein, In the description following and hereinafter R is de- R is one of the group OR or SR', in which R is fined as hereinabove. hydrogen, lower alkyl, cycloalkyl, lower alkenyl or The compounds of the present invention are prelower alkynyl. pared according to the following outlined synthesis:

CH pa a CH -C-Cl-l -Cl-l -CH -CH-CH -C=O (I) R' O O CH O PCH-C=CH-C-R (II) l R'O \L CH EH CH 0 Cll -C Cl-l -Cl-l -Cl-l l-l-CH -CH=CH-C=CH-C-R (A) The compounds of formula A are useful for the con- The esters of formula A (R is OR) are prepared by trol of insects. The utility of these compounds as insect the reaction of the aldehyde of formula I with the carbcontrol agents is believed to be attributable to their juanion of fon-nula II to yield a compound of formula A. venile hormone activity. They are preferably applied to 40 The carbanion (ii) is generated by treatment of the the immature insect, namely, during the embryo, larvae corresponding phosphonate with base, such as alkali or pupae stages in view of their effect on metamorphometal hydride or alkali metal alkoxide, e.g., sodium hysis and otherwise causing abnormal development leaddride, sodium ethoxide or sodium methoxide, in oring to death or to inability to reproduce. These comganic solvent inert to the reaction, such as hydrocarpounds are effective control agents for Heteropterans, bon, ether or dialkylsulfoxide solvent, e.g., benezene, such as Lygaeidae, Miridae and Pyrrhocoridae; Hotoluene, dimethylformamide, tetrahydrofuran, and the mopterans, such as Aphididae, Coccidae and Jassidae; like. The reaction is conducted at a temperature of Lepidopterans, such as Pyralidae, Noctuidae and Gelefrom about 20C to room temperature or above. The

chiidae; Coleopterans, such as Tenebrionidae, so phosphonates can be prepared as described by Patten- Crysomelidae and Dermestidae; Dipterans, such as Cuden et al., J. Chem. Soc. (C), 1984 and I997 (I968).

licidae, Muscidae and Sarcophagidae; and other in- The esters of formula A are converted into the corresects. The compounds can be applied at low dosage levsponding acid by hydrolysis with base, such as potasels of the order of 0.01 pg. to 10 pg. per insect. Suitsium carbonate or sodium carbonate in organic solvent,

able carrier substances include liquid or solid inert carsuch as methanol or ethanol. Other esters of the presriers, such as water, acetone, xylene, mineral or vegeta-' ent invention can be prepared by transesterification or ble oils, talc, vermiculite, natural and synthetic resins conversion of the acid into the acid halide by treatment and silica. Treatment of insects in accordance with the with thionyl chloride, oxalyl chloride, or the like, and present invention can be accomplished by spraying, then reacting the acid halide with the alcohol corredusting or otherwise contacting the insect, directly or sponding to the ester moiety desired.

indirectly, with one or more compounds offormula A. The thiolacid and thiolesters of formula A (R is Generally, a concentration of less than 25 percent of SR') are prepared from the acid chloride by reaction the active compound is employed. The formulations with hydrogen sulfide and alkylmercaptan or alkyl lead can include insect attractants, emulsifying agents or mercaptide, respectively.

wetting agents to assist in the application and effective- The term lower alkyl, as used herein, refers to a ness of the active ingredient. in the application of the straight or branched chain saturated aliphatic hydrocompounds, there is generally employed a mixture of carbon group having a chain length of one to six carbon atoms. cg, methyl. ethyl. propyl. n-butyl, s-butyl, thutyl. penlyl hexyl and i-propyl.

The term cycloalkyl". as used herein. refers to a cyclic alkyl group containing three to eight carbon atoms. e.g.. cyclopropyl. cyclopentyl and cyclohexyl.

The term lower alkenyl". as used herein. refers to an ethylenically unsaturated hydrocarbon group. branched or straight chain. having a chain length of two to six carbon atoms. e.g.. allyl. vinyl. B-butenyl. 2- hexenyl and i-propenyl.

The term lower alkynyl. as used herein. refers to an acetylenically unsaturated hydrocarbon group. branched or straight chain. having a chain length of three to six carbon atoms. e.g., 3-butynyl. Z-propynyl and K-pentynyl.

The presence of a double bond at position (-2 and C-4 of the compound of formula A gives rise to four isomers. each of which is embraced by the present invention. As mentioned above, a mixture of isomers is suitably employed for the control of insects. such as a mixture containing the transtZ), trans(4) isomer and the cis( 2). transt4) isomer. The conditions of the synthesis described herein and the reactants can be selected so as to favor formation of one isomer. such as the all trans isomer. over the formation of other isomers. The selection of appropriate conditions and reactants to favor formation of one isomer over another will be apparent to those of ordinary skill in the art. in the specific examples hereinafter. when isomerism is not specified, it is understood to include a mixture of isomers which. if desired. can be separated using known separation methods. such as chromatography or fractional distillation.

The following examples are provided to illustrate the present invention. Temperature is given in degrees Centigrade.

EXAMPLE l To a mixture of l g. of 3.7-dimethyl-7-octen-l-al (l) and L5 g. of phosphonate (ll: R' is ethyl. R is ethoxy) and 50 ml. of dimethylformamide. under nitrogen, is slowly added sodium ethoxide (prepared from 200 mg. of sodium and l2 ml. ethanol). The mixture is allowed to stand at room temperature for l hour. poured into water and extracted with ether. The ethereal extracts are dried, concentrated and then chromatographed on silica plates eluting with hexane/ether (5 percent ether) to yield ethyl 3.7.1 l-trimethyldodeca-2,4.l l-trienoate. which is predominantly trans at position C2.3 and C- 2.4.

EXAMPLE 2 A mixture of l g. of ethyl 3,7.l l-trimethyldodeca- 2.4.] l-trienoate. 60 ml. of methanol. 0.5 g. of sodium hydroxide and 6 ml. of water is stirred at about 30 for about 56 hours. The mixture is then diluted with water. acidified and extracted with ether. The organic phase is washed with water. dried over sodium sulfate and evaporated to yield 3.7.l Ltrimethyldodcca-ZAJ ltrienoic acid.

EXAMPLE 3 One gram ofthionyl chloride is added with stirring at room temperature to 0.5 g. of 3.7.1 l-trimethyldodeca 2.4.1 l-trienoic acid in 50 ml. of ether and the mixture heated at about 50 for minulelt. Excess thionyl chloride and solvent is removed by evtlhtlration and then fresh ether and cyclopropyl alcohol (about 2 equivalents) is added and the mixture allowed to stand 2 hours at room temperature. Excess cyclopropyl alcohol and solvent is removed by evaporation to yield cyclopropyl 3.7.l l-trimethyldodeca-2.4.l l-trienoate. which is purified by chromatography.

Similarly, by using other alcohols. such s-butanol. t-butanol. i-propanol. i-butanol. n-propanol, allyl alcohol or 3-pentynyl alcohol in the foregoing procedure. the corresponding esters are obtained.

EXAMPLE 4 One gram of 3.7.l l-trimethyldodeca-2.4.l l-trienoic acid in 30 ml. of benzene and 1 equivalent of sodium hydride is stirred about two hours and then a slight excess of oxalyl chloride is added at about 0 and stirred for 1 hour. The product is worked up by removal of solvent in vacuo and extraction with pentane to yield 3.7,- l l-trimethyldodeca-2,4.l l -trienoyl chloride.

EXAMPLE 5 To a solution of l2.7 g. of 3.7.] l-trimethyldodeca- 2.4.l l-trienoyl chloride in ether is added 6.2 g. ofethyl mercaptan and 5.9 g. of pyridine at -40. The mixture is allowed to stand at 0 for about 3 hours and then is diluted with ether and water and separated. The ether phase is washed with dilute aqueous sodium hydroxide, dilute hydrochloric acid and then water. dried and the solvent removed to yield ethyl 3.7.1 l-trimethylthiododeca-2.4.l l-trienoate.

Similarly. by using other mercaptans. such as methyl mercaptan. cyclohexyl mercaptan. i-propyl mercaptan. allyl mercaptan or B-butynyl mercaptan, the corresponding esters are obtained.

EXAMPLE 6 3,7,! l-Trimethyldodeca-2.4.l l-trienoyl chloride 17 g.) is added slowly to ethyl lead mercaptide (l3.4 g.) covered with ether. The mixture is allowed to stand overnight and then is filtered. The filtrate is evaporated under reduced pressure to yield ethyl 3.7.11- trimethylthioltrideca-Z.4.l l-trienoate, which can be purified by chromatography.

EXAMPLE 7 To 25 g. of 3.7.1l-trimethyldodeca-2.4,ll-trienoyl chloride in ether is added an excess of pyridine saturated with hydrogen sulfide at 40 and the mixture is allowed to stand in a sealed vessel at 0 for about 2 hours and then is diluted with water. neutralized and extracted with ether. The organic phase is washed with water. dried over sodium sulfate and evaporated to yield 3.7.1l-trimethylthiododeca-2.4.l l-trienoic acid.

EXAMPLE 8 Propargyl alcohol is reacted with 3.7.1]- trimethyldodeca-2.4.l l-trienoyl chloride using the process of Example 3 to yield prop-2yn-l-yl 3.7.l1- trimethyldodeca-2,4.l l-trienoate.

EXAMPLE 9 To dry NaHS (2.8 g.) in 40 ml of dry dimethylformamide, cooled in ice bath. is added 6.3 g. of 3.7.l ltrimethyldodeca-2.4.l l-trienoyl chloride. under nitrogen. The reaction is warmed to room temperature and stirred for 1.5 hours. The reaction is then poured into water. To the mixture is added about ml. ofetherlhexane l l and l percent NaOH and the neutral impurities extracted into the organic layer. The aqueous layer is acidified with 10 percent sulfuric acid solution and extracted 3X with ether/hexane. The combined organic layers are washed with water until neutral and with brine and dried over calcium sulfate. After filtering, solvents are evaporated leaving 3.7,] l-trimethylthiododeca-2,4,1 l-trienoic acid.

To a mixture of 3.5 g ofthe thioacid, 4.0 g. of prop-2- yn-l-yl chloride, 14 ml. ofether and 28 ml. of dimethylformamide, cooled to 5, is added 6.3 ml. of 2,4- lutidine. The reaction is then worked up by pouring into water and extracting 3X with ether. The combined organic layers are washed with 2N sulfuric acid, aqueous sodium bicarbonate, water until neutral. percent CuSO. solution, water and brine and then dried over calcium sulfate and solvent evaporated to yield prop- 2'-yn-l '-yl 3,7,] l-trimethylthioldodeca-2,4,l trienoate, which is purified by preparative thin-layer chromatography.

EXAMPLE [0 Into a flask equipped with an addition funnel. stirrer, thermometer and condenser is placed 32.1 g. of 50 percent aqueous NaOH and 200 ml. of ether. To this mixture is added 30.5 ml. of 97 percent ethanethiol in [0 ml. of ether. After addition is complete, the reaction is allowed to cool to ambient temperature, and to it is added, under nitrogen, a solution of 0.40 m. of 3,7,! ltrimethyldodeca-2.4,l ltrienoyl chloride in l00 ml. of ether. The reaction is stirred one hour at ambient temperature and then washed with ml. of 2N NaOH, 100 ml. of water and l00 ml. of brine. After drying over sodium sulfate. solvent is evaporated at reduced pressure to yield ethyl 3,7,l l-trimethylthioldodeca 2,4,l trienoate.

What is claimed is:

l. A compound selected from those of the following formula: 

1. A COMPOUND SELECTED FROM THOSE OF THE FOLLOWING FORMULA:
 2. A compound according to claim 1, wherein R'' is lower alkyl.
 3. A compound according to claim 1 wherein R'' is lower alkynyl.
 4. The compound, ethyl 3,7,11-trimethyldodeca-2,4,11-trienoate, according to claim
 1. 5. The compound, prop-2-yn-1-yl 3,7,11-trimethyldodeca-2,4,11-trienoate, according to claim
 3. 6. The trans,trans isomer of the compound of claim
 4. 7. A compound according to claim 1 wherein R'' is cyclopropyl. 